Oxidized polyacroleins as textile sizing agent



United States Patent US. Cl. 260--67 5 Claims Int. on. cost 3/40, 3/44, 3/46 ABSTRACT OF THE DISCLOSURE The use of the product of oxidizing polyacroleins in alkaline medium as sizing agents.

This invention relates to the sizing of yarns. It more particularly refers to a novel size for textile fibers.

It is known to size textile fibers or yarns in order to cause fibers protruding from the yarn to lay down and adhere to the remainder of the yarn. The size also imparts a smooth protective layer to the yarn and to the fibers thereof, which makes the yarn and fibers more resistant to mechanical wear, abrasion and shocks as may be encountered for example in a weaving process.

Many materials have been used in the past as sizes. These include starch, dextrin, glue, linseed oil, methyl cellulose, polyvinyl alcohol, arcylic and methacrylic acid polymer salts and many other materials.

It is known to apply antistatic agents to textiles in order to reduce the static charges thereon which build up when fibers or yarns are worked, particularly when such are Woven or passed over guide means in any operation. Many such antistatic agents are known and well documented in the art, for example, salts of polyacrylic acid.

It would be desirable to provide both protective and antistatic properties to textiles with a single material which can be applied as a sizing agent. This desirable result has been sought after by utilizing polyacrylic acid salts as a sizing agent for polyamides. It has been found that polyacrylic acid salts are generally good sizes, but that their antistatic properties are not as great as would be desirable.

It is therefore an object of this invention to provide a novel antistatic-protective sizing agent.

It is a further object of this invention to provide a process for reducing the static of textiles.

Other and additional objects of this invention will become apparent from a consideration of this entire specification including the claims appended hereto.

In accord with and fulfilling these objects, this invention includes, as one of its aspect, the provisions of a textile material, e.g., fiber, yarn, filament, fabric, etc. having as a size thereon a salt of the oxidation product of acrolein polymer, methacrolein polymer or copolymer of acrolein and methacrolein. The polymer prior to oxidation thereof has a molecular weight of about 1,000 to 50,000. The oxidation of the aldehyde groups of the poly mer is suitably at least about 70 percent complete. Generally it is not necessary to carry the oxidation of the aldehyde groups of the polymer to a greater degree of completion than about 98 percent.

Oxidized polyaldehydes useful in this invention are per se known materials. They have been produced in the past, for example, by oxidation with alkaline permanganate solutions (I. Am. Chem. Soc., 60 (1938), 1911) or in pyridine solution with hydrogen peroxide or po tassium permanganate (Ang. Chemie, 69 (1957), 162).

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However, it has been found to be particularly advantageous to proceed by using as oxidizing agent a mixture of cupric oxide or cupric hydroxide and a noble metal or noble metal oxide or noble metal hydroxide. The oxidation may be carried out upon the aldehyde polymer in aqueous suspension which may or may not have added thereto an organic solvent. Oxygen or oxygen-containing gases are preferably simultaneously introduced into the oxidation reaction; cf. in this connection German application D 45,008. It is possible to avoid the addition of noble metals or the earlier mentioned noble metal compounds by employing the polymerizates directly while they are still present in their mother liquor obtained during formation of the polymerizates.

Salts of the polymer oxidation products are exemplified by salts of sodium, potassium, ammonium or aliphatic amines, such as methylamine, diethylamine, etc., which are used in aqueous or aqueous-alcoholic solution. Noble metals which are useful in the oxidation of polyaldehydes include palladium, platinum, iridium, rhodium, ruthenium, etc.

Substantially any textile material can be treated with the oxidized polyaldehyde size of this invention. The greatest economic application of this invention is with respect to textiles which must be discharged of static or in which the tendency to build up static electricity charge should be suppressed, and to which it is desirable to apply protective size. It is particularly desirable to utilize this invention in connection with synthetic fibers such as polyamides, polyesters, acrylics, modacrylics, cellulosics, polyolefins, polyacetals, polybenzimidizoles and the like.

Since the oxidation of aldehydes generally leads to the production of carboxylic acids, it would be expected that the oxidation of polymers having pendant aldehyde groups would produce polymers having pendant carboxyl groups. Thus, the oxidation of polyacrolein might be expected to result in polyacrylic acids. It is not known exactly what the form of the oxidation product size of this invention is. It is surmised, however, that, since this oxidation product can be converted into a salt, there are probably present at least some carboxyl groups pendant from the polymer molecule. As noted above, polyacrylic acid has been used as a textile size. It is believed that the oxidation product of polyacrolein is in some way different from the polyacrylic acids used in the past, since, when these two materials are applied as sizing agents on identical fibers, the electrical properties of the sized fibers are substantially, in order of magnitude, different. For example, a nylon 66 yarn, which had an electrical field strength of about 30,000 volts per centimeter, when treated with a polyacrylic acid salt, had an electrical field strength of about 2,000 volts per centimeter. When the same yarn was treated with oxidized polyacrolein salt, the electrical field strength was reduced to about volts per centimeter. On the same comparative basis, the yarn electrical resistance was 1.5 X10 compared to an electrical resistance of 7 10 for the yarn sized with polyacrylic acid salt and 25x10 for the same yarn sized with oxidized polyacrolein salt.

It is within the scope of this invention to provide the oxidized polyacrolein, methacrolein or copolymer salt size described herein in combination with other known sizing agents, for example, polyacrylates, butyrals of polyacroleinformaldehyde and others.

The sizes of the instant invention are suitably applied to the textile being treated as an aqueous solution thereof. Other solvents besides water are suitable, but water is preferred. The size solution is suitably prepared in the concentrations known in the art and generally used, and such solutions are applied to the textile by known techniques.

The following examples are given by way of illustration of this invention and are in no way limiting thereon.

In each of the examples the polyacrolein was prepared in accord with the method of Houben-Weyl, Methoden dcr Organischen Chemie (Makromolekulate Stolfe), p. 5 1084 (1961, 4th ed.). The degree of oxidation was about 80 percent. In the following examples rovings were sized at a temperature of about 80 C. at a speed of about meters per minute. The oxidized polyacrolein was converted to the salt by reaction with 2 N-sodium hydroxide which was neutralized with 2 N-acetic acid to a pH of 7. The size was applied as an aqueous solution of the indi cated concentration.

EXAMPLE I The textile treated was a roving of polyester, formed by polycondensation of ethylene glycol and terephthalic acid, fibers 40 mm. in length of 1.5 denier per fiber. The oxidized polyacrolein size was applied as a 7-percentsolution as the sodium salt thereof.

TABLE I Roving Sized Roving Size, percent 5. 5 Loop tenacity 0. 87 0. 95=l=0. 05 Elongation 15. 35:1

EXAMPLE II The same polyester fibers as used in Example I were formed into a single spun yarn having a twist of 1100 turns per meter. The oxidized polyacrolein size was applied as a sodium salt solution of 4 weight percent concentration. The following comparative data was obtained upon testing of the sized and unsized yarn.

TABLE II Yarn Sized Yarn Size, percent 7. 6 Tenacity (qms.) 272:1:18 2913:19 Elongation, percent 21. 611. 4 21. 6;};1. 3 Mod us 3, 142 Electric field strength (volts/c 80 90 Electrical resistance (ohm 1X10 Abrasion resistance:

(N o. abrasion sequences) 4, 000

Sized with 5 weight percent carboxy methyl cellulose EXAMPLE III Example I was repeated using nylon 66 fibers. A 7% solution of size was used.

4 EXAMPLE v The textile treated was a roving of polyacrylonitrile fibers of 3 denier and varying lengths up to about 160 mm. The oxidized polyacrolein was applied as a sodium salt as a 7% solution.

TABLE V Roving Sized Roving Size, percent 9. 9 Loop tenacity 0.82 0. 66 Elongatlon 7. 7

EXAMPLE VI The same acrylic fibers as used in Example V were formed into a single spun yarn having a twist of 780 turns per meter. The oxidized polyacrolein was applied as a sodium salt solution of 3% concentration.

Sized with 2.5% carboxyrnethyl cellulose and 2.5% polyvinylalcohol 1, 400

What is claimed is:

1. A textile sizing agent comprising at least one watersoluble salt of a partially oxidized polymer of at least one member selected from the group consisting of acrolein, methacrolein and mixtures thereof, which polymer prior to oxidation thereof had a molecular weight of about 1,000 to 50,000 and which oxidation was carried out in an alkaline medium in the presence of a metallic oxidizing agent.

2. A sizing agent as claimed in claim 1 wherein the cation of said salt is at least one member selected from the group consisting of sodium, potassium, ammonium, methylamine and dimethylaminc.

3. A sizing agent as claimed in claim 1 wherein said polymer has been oxidized to about 70 to 98%.

4. A sizing agent as claimed in claim 1 wherein said oxidation has been carried out in the presence of a noble metal and a copper oxygen compound.

5. A textile having a sizing agent as claimed in claim 1 thereon.

References Cited UNITED STATES PATENTS 3,127,374 3/1964 Kern et-al. 260-67 WILLIAM H. SHORT, Primary Examiner.

L. M. PHYNES, Assistant Examiner.

US. Cl. X.R. 

